Synthesis and Characterization of Substituted Phosphasilenes and its Rare Homologue Stibasilene >Si=Sb.

Autor: Nazish M; Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany., Legendre CM; Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany., Herbst-Irmer R; Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany., Muhammed S; National Institute of Technology Calicut, Kozhikode, Kerala, 673601, India., Parameswaran P; National Institute of Technology Calicut, Kozhikode, Kerala, 673601, India., Stalke D; Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany., Roesky HW; Institut für Anorganische Chemie, Universität Göttingen, Tammannstraße 4, 37077, Göttingen, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Aug 21; Vol. 29 (47), pp. e202300791. Date of Electronic Publication: 2023 Jul 25.
DOI: 10.1002/chem.202300791
Abstrakt: Herein we report the reduction of R-EX 2 (E=P, Sb) with two equivalents of KC 8 in the presence of silylene (LSiR; L=PhC(NtBu) 2 ) to give Trip-P=SiL(C 6 H 4 PPh 2 ) (1), Ter Ph-P=(tBu)SiL (2) and Ter Ph-Sb=(tBu)SiL (3). The last (3) belongs to a new class of heavier analogues of Schiff bases (>C=N-), containing a formal >Si=Sb- double bond. The theoretical calculations suggest that lone pairs on the dicoordinated group-15 centers are stabilized by hyperconjugative interactions resulting in pseudo-Si-P/Si-Sb multiple bonds which are highly reactive as indicated by the high first and second proton affinities.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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